EP2155851A1 - Use of n-vinylimidazole polymers to improve the value-determining properties of biologic fermented solutions - Google Patents

Use of n-vinylimidazole polymers to improve the value-determining properties of biologic fermented solutions

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Publication number
EP2155851A1
EP2155851A1 EP08760390A EP08760390A EP2155851A1 EP 2155851 A1 EP2155851 A1 EP 2155851A1 EP 08760390 A EP08760390 A EP 08760390A EP 08760390 A EP08760390 A EP 08760390A EP 2155851 A1 EP2155851 A1 EP 2155851A1
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Prior art keywords
polymer
beer
value
prepared
determining properties
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EP08760390A
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German (de)
French (fr)
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EP2155851B1 (en
Inventor
Nikolaj Schmid
Gero Spika
Milan Jaron
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BASF SE
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BASF SE
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Priority to PL08760390T priority patent/PL2155851T3/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12H—PASTEURISATION, STERILISATION, PRESERVATION, PURIFICATION, CLARIFICATION OR AGEING OF ALCOHOLIC BEVERAGES; METHODS FOR ALTERING THE ALCOHOL CONTENT OF FERMENTED SOLUTIONS OR ALCOHOLIC BEVERAGES
    • C12H1/00—Pasteurisation, sterilisation, preservation, purification, clarification, or ageing of alcoholic beverages
    • C12H1/02—Pasteurisation, sterilisation, preservation, purification, clarification, or ageing of alcoholic beverages combined with removal of precipitate or added materials, e.g. adsorption material
    • C12H1/04—Pasteurisation, sterilisation, preservation, purification, clarification, or ageing of alcoholic beverages combined with removal of precipitate or added materials, e.g. adsorption material with the aid of ion-exchange material or inert clarification material, e.g. adsorption material
    • C12H1/0416—Pasteurisation, sterilisation, preservation, purification, clarification, or ageing of alcoholic beverages combined with removal of precipitate or added materials, e.g. adsorption material with the aid of ion-exchange material or inert clarification material, e.g. adsorption material with the aid of organic added material
    • C12H1/0424—Pasteurisation, sterilisation, preservation, purification, clarification, or ageing of alcoholic beverages combined with removal of precipitate or added materials, e.g. adsorption material with the aid of ion-exchange material or inert clarification material, e.g. adsorption material with the aid of organic added material with the aid of a polymer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/264—Synthetic macromolecular compounds derived from different types of monomers, e.g. linear or branched copolymers, block copolymers, graft copolymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
    • B01J20/267—Cross-linked polymers

Definitions

  • the patent application relates to the use of a crosslinked N-vinylimidazole polymer and a method for improving the value-determining properties of biological fermented solutions by treatment with a crosslinked polymer based on an N-vinylimidazole.
  • the process of making beer is essentially as follows: seasoning, fermentation, storage, filtration, stabilization, bottling.
  • seasoning obtained by roasting processes is fermented in the presence of brewers' yeast, followed by storage for a certain period of time, with secondary fermentation taking place.
  • This is usually followed by clarification of the beer to remove coarse particles, followed by a usually physical-chemical stabilization, be removed in the polyphenols and tannoids and proteins.
  • the clarification can be done for example by centrifugation, flotation or filtration. These separation techniques can be performed individually or in succession.
  • the thus stabilized ready-made beer or sales beer is then supplied to the bottling.
  • Römpp Chemielexikon 9th edition. Vol. 1, pp. 108-11 1, Georg Thieme Verlag, Stuttgart.
  • the quality of biologically fermented solutions such as beer and beer-like beverages is characterized by the sum of the value-determining properties.
  • value-determining properties one distinguishes the odor, taste, foam, microbiological and chemical-physical stability of the biologically fermented solutions and their drinkability.
  • Drinkability is an attribute of a drink due to its varietal taste and attractive for future consumption ("brand loyalty").
  • EP-A 88964 describes a process for the preparation of water-insoluble and only slightly swellable polymers of basic N-vinylheterocycles which can be used for the preparation of complexes with transition metals.
  • polymers based on basic vinyl heterocycles are used for removing heavy metals from wine and wine-type beverages.
  • the polymers should be able to be regenerated after treatment with dilute mineral acids.
  • EP-A 781 787 describes the use of water-insoluble and only slightly swellable polymers of basic N-vinylheterocycles for the preparation of complexes with heavy metal ions.
  • the complexes with heavy metal ions are said to serve to remove sulphurous compounds from wine and wine-like beverages.
  • the main task was to ensure an improved flavor profile right from the start.
  • This object is achieved by a method for improving the value-determining properties of biological fermented solutions, which is characterized in that the biologically fermented solution per 100 liters with 1 to 3000 g of a polymer of 50-99.5 wt.% N Vinylimidazole 0 to 49.5% by weight copolymerized with another copolymerizable monomer and is prepared in the absence of oxygen and of polymerization initiators and in the presence of from 0.5 to 10% by weight, based on the monomers, of a crosslinker.
  • the invention also provides the use of an N-vinylimidazole polymer for improving the value-determining properties.
  • Biologically fermented liquids according to the invention are in particular beer and beer-like drinks.
  • the beer product is a beer intermediate, which is not a finished or sold beer.
  • the beer product has not yet been subjected to clarification or physical-chemical stabilization.
  • a non-filtrate can be treated directly after fermentation and secondary fermentation, ie before clarification and / or physico-chemical stabilization, treated. It may also be advisable to use the polymer to be used according to the invention in the preceding production steps, such as water treatment, mashing, wort production or fermentation. According to a further embodiment, the treatment can be carried out together with the first filtration step after fermentation and secondary fermentation.
  • the amount of polymer used is 1 to 3000, preferably 50 g to 200, more preferably 40 to 80 g per 100 I.
  • the N-vinylimidazole polymer can be added as a solid or added in the form of an aqueous suspension.
  • the solids content of the suspension can be 1 to 30, in particular 5 to 10 wt .-%.
  • the N-vinyl polymer used contains 70 to 99.5 wt .-% N-
  • Vinylimidazole 0 to 29.5 wt .-% of the copolymerizable monomer and 0.5 to 10 wt .-% of the crosslinking agent.
  • Copolymers of 50 to 99.5% by weight of N-vinylimidazole and N-vinylpyrrolidone as comonomer are also preferred.
  • Preferred crosslinkers are N, N'-divinylimidazolidin-2-one.
  • Very particular preference is given to a polymer of 90% by weight of N-vinylimidazole, 7% by weight of N-vinylpyrrolidone and 3% by weight of N, N'-divinylimidazolin-2-one.
  • the data in% by weight relate to the total amount of monomers and crosslinkers.
  • N-vinyl polymers used according to the invention are commercially available, for example as Divergan® HM from BASF.
  • the treatment according to the invention can be carried out like a filtration.
  • the polymer can be used, for example, as in the patent application DE 19547761 A1 as bulk material for the precoat filtration.
  • the polymerized vinyl heterocycle can be used both as a so-called pre-flow coating or in a continuous dosage in the precoat filtration.
  • the matrix described above may consist of the following materials: synthetic polymers such as polyethylene, polypropylene, polybutylene, polyamide, polystyrene, polyethersulfones or polyesters, celluloses, inorganic materials such as kieselguhr, perlites, asbestos, glass, aluminas, silicas, activated carbon and / or sand , or resins.
  • the quantitative ratio of N-vinylimidazole polymer to matrix materials is usually 1:10 to 1: 1.
  • the raw beer products treated according to the invention are assessed with regard to their taste stability.
  • Beer flavorings (alcohols, esters, acids)
  • the chemical-physical stability can be investigated by determining the content of tannoids, proteins and total polyphenols.
  • N-vinylimidazole polymer makes it possible to achieve in a simple way a stabilization of the crude fermented product, which has the consequence that the formation of aging substances is later suppressed during storage and transport of the finished sales product.
  • inventive method takes place at a time, due to the highly complex chemical Composition and the still present yeasts still takes place an aroma formation.
  • Adsorption of heavy metal ions such as copper or iron or aluminum ions in the unfiltered material can influence the flavor profile.
  • phenolic components such as 3,4-dihydroxycinnamic acid
  • these compounds can be removed from conversion by enzymatic reactions and thus the flavor profile can be positively influenced.
  • the process according to the invention does not replace the subsequent filtration by means of a filter aid to remove coarser particles or cell residues, nor stabilization with e.g. Silica, crosslinked polyvinylpyrrolidones and similar substances.
  • the formation of the flavoring substances and the chemical composition important for aging stability with regard to the typical aging indicators are influenced.
  • test specifications given in the following examples refer to the analytical requirements available at the Technical University of Kunststoff, Department of Technology Brewery I, Weihenstephan, which are also available on request, which also comply with the requirements of the Central European Brewing Analysis Commission (MEBAK).
  • MEBAK Central European Brewing Analysis Commission
  • the treatment took place in an industrial pilot plant. Treated were 50 l of a beer unfiltered type of Pilsner beer. In this case, 20 g, 40 g or 80 g of Divergan HM per 100 l of unfiltrate were metered in during the filtration with Kieseiguhr (Becogur®).
  • the DLG tasting scheme judges the beers on a five-point scale, with 5 being pure and no tasteless taste. It is advisable to carry out the evaluation in 0.5-point increments.
  • Eichhorn designed a tasting scheme for the sensory evaluation of aged beers.
  • This scheme only the freshness or degree of aging of a beer is assessed.
  • the criteria are based on those of the DLG scheme, whereby only smell, taste and the quality of the bitterness are evaluated.
  • Grades ranging from 1 to 4 can be given as the rating scale for aging taste.
  • the grade 1 is unrestricted fresh and 4 extremely aged.
  • the tasters judge the acceptance in percent. For example, an acceptance score of 20% means that only every 5th taster would accept this beer. In advance, it is essential to train the taster panel on aging taste.
  • the beers are forcibly aged.
  • the samples are shaken for 24 hours to simulate the distribution channel and then stored dark at 40 0 C for 4 days.
  • the tasting is fresh against forced.
  • For sensory evaluation of the taste stability is according to the 5-point scheme of DLG tastes and in addition the aging state according to Eichhorn is evaluated with a 4-point scaling.
  • naturally stored beers can and should be regularly tasted for aging.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Biochemistry (AREA)
  • Genetics & Genomics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Food Science & Technology (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • General Engineering & Computer Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Distillation Of Fermentation Liquor, Processing Of Alcohols, Vinegar And Beer (AREA)
  • Non-Alcoholic Beverages (AREA)
  • Measuring Or Testing Involving Enzymes Or Micro-Organisms (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention relates to a method for improving the value-determining properties of biologic fermented solutions, characterized in that the biologic fermented solution is treated per liter with 1 to 3000 g of a polymer after fermentation, comprising polymerized therein 50-99.5 wt.% of N-vinylimidazole and 0 to 49.5 wt.% of another copolymerizable monomer and is produced in the absence of oxygen and polymerization inhibitors and in the presence of 0.5 to 10 wt.% of a crosslinking agent, relative to the monomers.

Description

Verwendung eines N-Vinylimidazol-Polymerisats zur Verbesserung der wertbestimmenden Eigenschaften von biologischen fermentierten Lösungen Beschreibung Use of an N-vinylimidazole polymer to improve the value-determining properties of biological fermented solutions Description
Die Patentanmeldung betrifft die Verwendung eines quervernetzten N-Vinylimidazol- Polymerisats sowie ein Verfahren zur Verbesserung der wertbestimmenden Eigenschaften von biologischen fermentierten Lösungen durch Behandlung mit einem quervernetzten Polymerisat auf Basis eines N-Vinylimidazols.The patent application relates to the use of a crosslinked N-vinylimidazole polymer and a method for improving the value-determining properties of biological fermented solutions by treatment with a crosslinked polymer based on an N-vinylimidazole.
Durch den Einsatz des qurvernetzten N-Vinylimidazol-Polymerisats werden biologisch fermentierte Lösungen in ihren wertbestimmenden Eigenschaften verbessert.By using the qurneted N-vinylimidazole polymer, biologically fermented solutions are improved in their value-determining properties.
Der Prozess der Herstellung von Bier verläuft im wesentlichen wie folgt: Würzenbereitung, Gärung, Lagerung, Filtration, Stabilisierung, Abfüllung. Die durch Röstverfahren gewonnene Würze wird in Gegenwart von Bierhefen vergoren, woran sich eine Lagerung für einen bestimmten Zeitraum, wobei eine Nachgärung stattfindet, anschliesst. Danach erfolgt üblicherweise eine Klärung des Bieres, um grobe Partikel zu entfernen, woran sich eine üblicherweise physikalische-chemische Stabilisierung anschliesst, bei der Polyphenole und Tannoide sowie Eiweißstoffe entfernt werden. Die Klärung kann beispielsweise durch Zentrifugation, Flotation oder Filtration erfolgen. Diese Trenntechniken können einzeln oder hintereinander durchgeführt werden. Das solchermas- sen stabilisierte Fertigbier oder Verkaufsbier wird dann der Abfüllung zugeführt. Zur Herstellung von Bieren und ähnlichen alkoholischen Getränken siehe auch Römpp Chemielexikon, 9. Auflage. Bd. 1 , S. 108-11 1 , Georg Thieme Verlag, Stuttgart.The process of making beer is essentially as follows: seasoning, fermentation, storage, filtration, stabilization, bottling. The seasoning obtained by roasting processes is fermented in the presence of brewers' yeast, followed by storage for a certain period of time, with secondary fermentation taking place. This is usually followed by clarification of the beer to remove coarse particles, followed by a usually physical-chemical stabilization, be removed in the polyphenols and tannoids and proteins. The clarification can be done for example by centrifugation, flotation or filtration. These separation techniques can be performed individually or in succession. The thus stabilized ready-made beer or sales beer is then supplied to the bottling. For the production of beers and similar alcoholic beverages see also Römpp Chemielexikon, 9th edition. Vol. 1, pp. 108-11 1, Georg Thieme Verlag, Stuttgart.
Durch die Stoffwechselaktivität der Hefe werden im Verlauf der Gärung neben Ethanol eine Vielzahl von aromaintensiven, leichtflüchtigen Substanzen gebildet. Diese Gärungsnebenprodukte sind in der Hauptsache Alkohole und Ester.Through the metabolic activity of yeast, a large number of flavor-intensive, volatile substances are formed in the course of fermentation in addition to ethanol. These fermentation by-products are mainly alcohols and esters.
Die Qualität von biologisch fermentierten Lösungen wie beispielsweise Bier und bierähnliche Getränke) ist gekennzeichnet durch die Summe der wertbestimmenden Eigenschaften. Bei den wertbestimmenden Eigenschaften unterscheidet man Geruchs-, Geschmacks-, Schaum-, mikrobiologischen und chemisch-physikalischen Stabilität der biologisch fermentierten Lösungen sowie deren Drinkability. Drinkability bezeichent ein Atribut eines Getränks durch seinen sortentypischen Geschmack auch für den zukünftigen Konsum attraktiv zu sein („Markentreue").The quality of biologically fermented solutions such as beer and beer-like beverages is characterized by the sum of the value-determining properties. In the value-determining properties one distinguishes the odor, taste, foam, microbiological and chemical-physical stability of the biologically fermented solutions and their drinkability. Drinkability is an attribute of a drink due to its varietal taste and attractive for future consumption ("brand loyalty").
Diese wertbestimmenden Eigenschaften sollten sich während der Lagerung und des Transportes nicht nachteilig verändern. Durch verschiedene Parameter werden die Eigenschaften während der Lagerung jedoch verändert. Dazu gehören beispielsweise autoxidative Veränderungen, Energieeintrag durch Licht oder Transport und auch der Anteil an bestimmten nach der Gärung vorhandenen Inhaltsstoffen wie beispielsweise- Fettsäuren, Zucker oder Aminosäuren.These value-determining properties should not be adversely affected during storage and transportation. However, various parameters change the properties during storage. These include, for example, autoxidative changes, energy input by light or transport and also the Share of certain post-fermentation ingredients such as fatty acids, sugars or amino acids.
Zur physikalischen Klärung des Bieres werden häufig Mineralstoffe wie Kieselgur, Per- lite oder Bentonit verwendet. Zur Entfernung von Polyphenolen kann beispielsweise quervernetztes Polyvinylpyrrolidon verwendet werden. Zur Entfernung von Proteinen wird auch Silica eingesetzt.For the physical clarification of beer, minerals such as kieselguhr, perlite or bentonite are often used. Crosslinked polyvinyl pyrrolidone, for example, can be used to remove polyphenols. Silica is also used to remove proteins.
Es ist auch bekannt, den Filtrationsschritt mit dem Stabilisierungsschritt zu kombinieren, indem Filterhilfsmittel eingesetzt werde, die gleichzeitig eine mechanische Abtren- nung von Hefezellen und eine Stabilisierung ermöglichen.It is also known to combine the filtration step with the stabilization step by using filter aids which simultaneously enable mechanical separation of yeast cells and stabilization.
In der EP-A 88964 ist ein Verfahren zur Herstellung von in Wasser unlöslichen und nur wenig quellbaren Polymeren aus basischen N-Vinylheterocyclen beschrieben, die zur Herstellung von Komplexen mit Übergangsmetallen verwendet werden können.EP-A 88964 describes a process for the preparation of water-insoluble and only slightly swellable polymers of basic N-vinylheterocycles which can be used for the preparation of complexes with transition metals.
Gemäß EP-A-4 38 713 werden Polymerisate auf Basis von basischen Vinylheterocyc- len zur Entfernung von Schwermetallen aus Wein und weinähnlichen Getränken eingesetzt. Die Polymerisate sollen nach der Behandlung mit verdünnten Mineralsäuren regeneriert werden können.According to EP-A-4 38 713, polymers based on basic vinyl heterocycles are used for removing heavy metals from wine and wine-type beverages. The polymers should be able to be regenerated after treatment with dilute mineral acids.
In der EP-A 781 787 ist die Verwendung von in Wasser unlöslichen und nur wenig quellbaren Polymerisaten aus basischen N-Vinylheterocyclen zur Herstellung von Komplexen mit Schwermetallionen beschrieben. Die Komplexe mit Schwermetallionen sollen zur Entfernung von schwefelhaltigen Verbindungen aus Wein und weinähnlichen Getränken dienen.EP-A 781 787 describes the use of water-insoluble and only slightly swellable polymers of basic N-vinylheterocycles for the preparation of complexes with heavy metal ions. The complexes with heavy metal ions are said to serve to remove sulphurous compounds from wine and wine-like beverages.
Aus der EP-A 642 521 ist bekannt, Aluminiumionen aus Getränken wie Bier, Wein, weinähnlichen Getränken oder Fruchtsaft zu entfernen. Allerdings bezieht sich die darin beschriebene Behandlung von Bier auf ein fertiges Verkaufsbier, dass vorher bereits einer physikalisch-chemischen Stabilisierung unterzogen worden war. Durch die in diesem Dokument beschriebene Behandlung wurde das sortentypische Aroma nicht beeinflusst.From EP-A 642 521 it is known to remove aluminum ions from beverages such as beer, wine, wine-like drinks or fruit juice. However, the treatment of beer described therein refers to a finished sales beer that had previously undergone physicochemical stabilization. The treatment described in this document did not affect the varietal aroma.
Der Erfindung lag daher die Aufgabe zugrunde, ein verbessertes Verfahren zur Ver- besserung der wertbestimmenden Eigenschaften, insbesondere des Aromaprofils, von Bier und bierähnlichen Getränken zu entwickeln. Aufgabe war es vor allem, von vorne- herein für ein verbessertes Aromaprofil zu sorgen.It was therefore an object of the invention to develop an improved process for improving the value-determining properties, in particular of the flavor profile, of beer and beer-like beverages. The main task was to ensure an improved flavor profile right from the start.
Diese Aufgabe wird gelöst durch ein Verfahren zur Verbesserung der wertbestimmen- den Eigenschaften von biologischen fermentierten Lösungen, welches dadurch gekennzeichnet ist, dass man die biologisch fermentierte Lösung pro 100 Liter mit 1 bis 3000 g eines Polymerisates aus 50-99,5 Gew.% N-Vinylimidazol 0 bis 49,5 Gew.% eines anderen copolymerisierbaren Monomeren einpolymerisiert enthält und unter Ausschluß von Sauerstoff und von Polymerisationsinitiatoren sowie in Gegenwart von 0,5 bis 10 Gew. %, bezogen auf die Monomeren, eines Vernetzers hergestellt wird, behandelt.This object is achieved by a method for improving the value-determining properties of biological fermented solutions, which is characterized in that the biologically fermented solution per 100 liters with 1 to 3000 g of a polymer of 50-99.5 wt.% N Vinylimidazole 0 to 49.5% by weight copolymerized with another copolymerizable monomer and is prepared in the absence of oxygen and of polymerization initiators and in the presence of from 0.5 to 10% by weight, based on the monomers, of a crosslinker.
Gegenstand der Erfindung ist auch die Verwendung eines N-Vinylimidazol- Polymerisats zur Verbesserung der wertbestimmenden Eigenschaften.The invention also provides the use of an N-vinylimidazole polymer for improving the value-determining properties.
Biologisch fermentierte Flüssigkeiten sind erfindungsgemäß insbesondere Bier und bierähnliche Getränke. Als Bierprodukt wird eine Bierzwischenstufe bezeichnet, die kein Fertig- oder Verkaufsbier darstellt. Das Bierprodukt ist noch keiner Klärung oder physikalisch-chemischen Stabilisierung zugeführt worden.Biologically fermented liquids according to the invention are in particular beer and beer-like drinks. The beer product is a beer intermediate, which is not a finished or sold beer. The beer product has not yet been subjected to clarification or physical-chemical stabilization.
Die Behandlung nach dem erfindungsgemäßen Verfahren kann ein Unfiltrat direkt nach der Gärung und Nachgärung, also vor der Klärung und/oder physikalisch-chemischen Stabilisierung erfolgen, behandelt werden. Es kann sich auch empfehlen, dass erfindungsgemäß zu verwendende Polymerisat in den vorgeschalteten Produktionsschritten wie der Wasserbehandlung, Maischen, Würzeherstellung oder Gärung einzusetzen. Gemäß einer weiteren Ausführungsform kann die Behandlung zusammen mit dem ersten Filtrationsschritt nach der Gärung und Nachgärung erfolgen.The treatment by the process according to the invention, a non-filtrate can be treated directly after fermentation and secondary fermentation, ie before clarification and / or physico-chemical stabilization, treated. It may also be advisable to use the polymer to be used according to the invention in the preceding production steps, such as water treatment, mashing, wort production or fermentation. According to a further embodiment, the treatment can be carried out together with the first filtration step after fermentation and secondary fermentation.
Die Menge an verwendetem Polymerisat beträgt 1 bis 3000, bevorzugt 50 g bis200, besonders bevorzugt 40 bis 80 g pro 100 I.The amount of polymer used is 1 to 3000, preferably 50 g to 200, more preferably 40 to 80 g per 100 I.
Das N-Vinylimidazol-Polymerisat kann als Feststoff zugegeben werden oder in Form einer wässrigen Suspension zudosiert werden. Der Feststoffgehalt der Suspension kann 1 bis 30, insbesondere 5 bis 10 Gew.-% betragen.The N-vinylimidazole polymer can be added as a solid or added in the form of an aqueous suspension. The solids content of the suspension can be 1 to 30, in particular 5 to 10 wt .-%.
Die Herstellung der erfindungsgemäß eingesetzten N-Vinyl-Polymerisate ist an sich bekannt und in der EP-A 88964, der EP-A 438713 und der EP-A 642521 ausführlich beschrieben und es wird diesbezüglich hiermit ausdrücklich auf die Offenbarung der genannten Schriften Bezug genommen.The preparation of the N-vinyl polymers used according to the invention is known per se and described in detail in EP-A 88964, EP-A 438713 and EP-A 642521 and reference is hereby expressly made to the disclosure of said documents.
Bevorzugt enthält das verwendete N-Vinyl-Polymerisat 70 bis 99.5 Gew.-% N-Preferably, the N-vinyl polymer used contains 70 to 99.5 wt .-% N-
Vinylimidazol, 0 bis 29.5 Gew.-% des copolymerisierbaren Monomeren und 0.5 bis 10 Gew.-% des Vernetzers.Vinylimidazole, 0 to 29.5 wt .-% of the copolymerizable monomer and 0.5 to 10 wt .-% of the crosslinking agent.
Bevorzugt werden weiterhin Copolymere aus 50 bis 99.5 Gew.-% N-Vinylimidazol und N-Vinylpyrrolidon als Comonomer. Als Vernetzer kommt bevorzugt N, N'- Divinylimidazolidin-2-on Betracht. Ganz besonders bevorzugt ist ein Polymerisat aus 90 Gew.-% N-Vinylimidazol, 7 Gew.-% N-Vinylpyrrolidon und 3 Gew.-% N,N'-Divinylimidazolin-2-on.Copolymers of 50 to 99.5% by weight of N-vinylimidazole and N-vinylpyrrolidone as comonomer are also preferred. Preferred crosslinkers are N, N'-divinylimidazolidin-2-one. Very particular preference is given to a polymer of 90% by weight of N-vinylimidazole, 7% by weight of N-vinylpyrrolidone and 3% by weight of N, N'-divinylimidazolin-2-one.
Die Angaben in Gew.-% beziehen sich dabei auf die Gesamtmenge an Monomeren und Vernetzer.The data in% by weight relate to the total amount of monomers and crosslinkers.
Die erfindungsgemäß verwendetenen N-Vinyl-Polymerisate sind zum Teil kommerziell erhältlich, beispielsweise als Divergan® HM der Firma BASF.Some of the N-vinyl polymers used according to the invention are commercially available, for example as Divergan® HM from BASF.
Verfahrenstechisch kann die erfindungstechnische Behandlung wie eine Filtration durchgeführt werden. Das Polymerisat kann beispielsweise wie in der Patentanmeldung DE 19547761 A1 als Schüttgut für die Anschwemmfiltration verwendet werden. Das polymerisiertes Vinylheterocyclus kann sowohl als sogenannte Voranschwemm- schicht oder bei einer laufenden Dosage bei der Anschwemmfiltration zum Einsatz kommen.In terms of process technology, the treatment according to the invention can be carried out like a filtration. The polymer can be used, for example, as in the patent application DE 19547761 A1 as bulk material for the precoat filtration. The polymerized vinyl heterocycle can be used both as a so-called pre-flow coating or in a continuous dosage in the precoat filtration.
Ferner ist es möglich das Polymerisat in verschiedenen Formen in einer Matrix einzuarbeiten, beispielsweise in Filterkerzen, Filtermodulen, Filterschichten, Membranen oder lonentauschersäulen. Die oben beschriebene Matrix kann aus den folgenden Materialien bestehen: synthetische Polymere wie Polyethylen, Polyproylen, Polybutylen, Polyamid, Polystyrol, Polyethersulfone oder Polyester, Cellulosen, anorganischen Materialien wie Kieselgur, Perlite, Asbest, Glas, Aluminiumoxide, Siliciumoxide, Aktivkohle und/oder Sand, oder Harze.It is also possible to incorporate the polymer in various forms in a matrix, for example in filter cartridges, filter modules, filter layers, membranes or ion exchange columns. The matrix described above may consist of the following materials: synthetic polymers such as polyethylene, polypropylene, polybutylene, polyamide, polystyrene, polyethersulfones or polyesters, celluloses, inorganic materials such as kieselguhr, perlites, asbestos, glass, aluminas, silicas, activated carbon and / or sand , or resins.
Bei der Einarbeitung in eine Matrix beträgt das Mengenverhältnis von N-Vinylimdazol- Polymerisat zu Matrixmaterialien üblicherweise 1 : 10 bis1 :1.When incorporated into a matrix, the quantitative ratio of N-vinylimidazole polymer to matrix materials is usually 1:10 to 1: 1.
Die erfindungsgemäß behandelten Roh-Bierprodukte werden hinsichtlich ihrer Geschmackstabilität beurteilt.The raw beer products treated according to the invention are assessed with regard to their taste stability.
Zur Beurteilung des Geschmackstabilität sind grundsätzlich zwei Methoden zu unter- scheiden:There are basically two methods for assessing the taste stability:
1. Die analytische Beurteilung mittels Gaschromatographie, HPLC, and ESR und1. The analytical evaluation by gas chromatography, HPLC, and ESR and
2. die sensorische Beurteilung durch verschiedenen Verkostungsschemata wie z.B. Verkostung nach DLG oder nach Eichhorn.2. the sensory evaluation by various tasting schemes, e.g. Tasting according to DLG or Eichhorn.
Folgende Analysenmethoden können bei der Messung der Geschmacksstabilität zum Einsatz kommen: 1. Höhere aliphatische Alkohole und leichflüchtige EsterThe following analytical methods can be used in the measurement of the taste stability: 1. Higher aliphatic alcohols and volatile esters
2. Bieraromastoffe (Alkohole, Ester, Säuren)2. Beer flavorings (alcohols, esters, acids)
3. Alterungsindikatoren (Wärme-, Sauerstoffindikatoren, Alterungskomponenten) 4. Stabilitätsindex3. Aging indicators (heat, oxygen indicators, aging components) 4. Stability index
5. Verkostung nach DLG5. Tasting according to DLG
6. Verkostung nach Eichhorn6th tasting to Eichhorn
Weiterhin kann auch die chemisch-physikalischen Stabilität über die Bestimmung des Gehalts an Tannoiden, Proteine und Gesamtpolyphenolen untersucht werden.Furthermore, the chemical-physical stability can be investigated by determining the content of tannoids, proteins and total polyphenols.
Durch die erfindungsgemäße Verwendung eines N-Vinylimidazol-Polymerisats ist es möglich, auf einfache Weise eine Stabilisierung des rohen fermentierten Produkts zu erzielen, die zur Folge hat, dass später bei Lagerung und Transport des fertigen Ver- kaufsprodukt die Bildung von Alterungsstoffen zurückgedrängt wird. Im Gegensatz zu den im Stand der Technik beschriebenen Verfahren, die nur auf eine Klärung oder Nachbehandlung eines fertigen Getränks abzielen, also zu einem Zeitpunkt an dem die Aromabildung im wesentlichen abgeschlossen ist, greift das erfindungsgemäße Verfahren zu einem Zeitpunkt, zu dem aufgrund der hochkomplexen chemischen Zusammen- Setzung und der noch anwesenden Hefen noch eine Aromabildung stattfindet. Durch die Adsorption von Schwermetallionen wie Kupfer oder Eisen oder von Aluminiumionen im Unfiltrat kann das Aromaprofil beeinflusst werden. Durch die Adsorption von phenolischen Komponenten wie beispielsweise 3,4-Dihydroxyzimtsäure, können diese Verbindungen einer Umwandlung durch enzymatische Reaktionen entzogen und damit das Aromaprofil positiv beeinflusst werden. Das erfindungsgemäße Verfahren ersetzt nicht die spätere Filtration mittels eines Filterhilfsmittels zur Entfernung gröberer Partikel oder Zellreste und auch nicht die Stabilisierung mit z.B. Silica, vernetzten Polyvinyl- pyrrolidonen und ähnlichen Substanzen. Erfindungsgemäß wird insbesondere die Ausbildung der Aromastoffe und der für eine Alterungsstabilität hinsichtlich der typischen Alterungsindikatoren wichtigen chemischen Zusammensetzung beeinflusst.The use according to the invention of an N-vinylimidazole polymer makes it possible to achieve in a simple way a stabilization of the crude fermented product, which has the consequence that the formation of aging substances is later suppressed during storage and transport of the finished sales product. In contrast to the methods described in the prior art, which are aimed only at a clarification or aftertreatment of a finished beverage, ie at a time at which the aroma formation is substantially complete, the inventive method takes place at a time, due to the highly complex chemical Composition and the still present yeasts still takes place an aroma formation. Adsorption of heavy metal ions such as copper or iron or aluminum ions in the unfiltered material can influence the flavor profile. By adsorption of phenolic components such as 3,4-dihydroxycinnamic acid, these compounds can be removed from conversion by enzymatic reactions and thus the flavor profile can be positively influenced. The process according to the invention does not replace the subsequent filtration by means of a filter aid to remove coarser particles or cell residues, nor stabilization with e.g. Silica, crosslinked polyvinylpyrrolidones and similar substances. According to the invention, in particular, the formation of the flavoring substances and the chemical composition important for aging stability with regard to the typical aging indicators are influenced.
Es war für den Fachmann überraschend, dass mit einer Behandlung direkt nach der Gärung später auch eine größere Stabilität des fertigen Produkts hinsichtlich der wertbestimmenden Eigenschaften erzielt werden kann.It was surprising for the skilled worker that with a treatment directly after the fermentation later a greater stability of the finished product with regard to the value-determining properties can be achieved.
BeispieleExamples
Die in den folgenden Beispielen genannten Prüfvorschriften beziehen sich auf die bei der TU München, Lehrstuhl für Technologie der Brauerei I, Weihenstephan, fürjeder- mann auf Anfrage erhältlichen Analysenvorschriften, die auch den Vorschriften der Mitteleuropäischen Brauanalysen-Komission MEBAK entsprechen. Die Behandlung erfolgte in einer industriellen Pilot-Anlage. Behandelt wurden 50 I eines Bier-Unfiltrats vom Typ eines Pilsner-Bieres. Dabei wurden 20 g, 40 g oder 80 g Diver- gan HM pro 100 I Unfiltrat bei der Filtration mit Kieseiguhr (Becogur®) zudosiert.The test specifications given in the following examples refer to the analytical requirements available at the Technical University of Munich, Department of Technology Brewery I, Weihenstephan, which are also available on request, which also comply with the requirements of the Central European Brewing Analysis Commission (MEBAK). The treatment took place in an industrial pilot plant. Treated were 50 l of a beer unfiltered type of Pilsner beer. In this case, 20 g, 40 g or 80 g of Divergan HM per 100 l of unfiltrate were metered in during the filtration with Kieseiguhr (Becogur®).
Analytische BeurteilungAnalytical assessment
Bestimmung der Alterungsindikatoren Prüfverfahren Nr. GC007/96 Ergebnisse siehe Tabelle 1Determination of aging indicators Test Method No GC007 / 96 For results see Table 1
Höhere aliphatische Alkohole und leichtflüchtige Ester Prüfverfahren Nr. GC008/96 Ergebnisse siehe Tabelle 2Higher Aliphatic Alcohols and Volatile Esters Test Method No. GC008 / 96 See Table 2 for results
Sensorische BeurteilungSensory assessment
Verkostung nach DLGTasting according to DLG
Das DLG-Verkostungsschema beurteilt die Biere in einer Fünf-Punkte-Skala, wobei 5 rein und ohne Fehlgeschmack bedeutet. Es bietet sich an die Bewertung in 0,5-Punkte- Schritten vorzunehmen.The DLG tasting scheme judges the beers on a five-point scale, with 5 being pure and no tasteless taste. It is advisable to carry out the evaluation in 0.5-point increments.
Alterungsverkostung nach EichhornAging tasting after Eichhorn
Eichhorn entwarf ein Verkostungsschema zur sensorischen Beurteilung gealterter Biere. Bei diesem Schema wird ausschließlich die Frische beziehungsweise der Alte- rungsgrad eines Bieres beurteilt. Die Kriterien orientieren sich dabei an denen des DLG-Schemas, wobei nur Geruch, Geschmack und die Qualität der Bittere bewertet werden. Als Skala zur Bewertung des Alterungsgeschmacks können Noten zwischen 1 und 4 gegeben werden. Dabei steht die Note 1 für uneingeschränkt frisch und 4 für extrem gealtert. Weiterhin wird durch die Verkoster die Akzeptanz in Prozent beurteilt. Beispielsweise bedeutet ein Akzeptanzwert von 20 %, dass nur jeder 5. Verkoster dieses Bier akzeptieren würde. Im Vorfeld ist es unerlässlich, das Verkosterpanel auf Alterungsgeschmack zu trainieren.Eichhorn designed a tasting scheme for the sensory evaluation of aged beers. In this scheme, only the freshness or degree of aging of a beer is assessed. The criteria are based on those of the DLG scheme, whereby only smell, taste and the quality of the bitterness are evaluated. Grades ranging from 1 to 4 can be given as the rating scale for aging taste. The grade 1 is unrestricted fresh and 4 extremely aged. Furthermore, the tasters judge the acceptance in percent. For example, an acceptance score of 20% means that only every 5th taster would accept this beer. In advance, it is essential to train the taster panel on aging taste.
Zur Vorhersage der Geschmackstabilität werden die Biere forciert gealtert. Die Proben werden hierzu 24 Stunden geschüttelt, um den Vertriebsweg zu simulieren und danach 4 Tage bei 40 0C dunkel gelagert. Die Verkostung erfolgt frisch gegen forciert. Zur sensorischen Beurteilung der Geschmacksstabilität wird nach dem 5-Punkte-Schema der DLG verkostet und zusätzlich wird der Alterungszustand nach Eichhorn mit einer 4- Punkte-Skalierung bewertet. Alternativ zur forcierten Alterung können und sollten natürlich gelagerte Biere (Rückstellproben) regelmäßig auf Alterung hin verkostet werden.To forecast the taste stability, the beers are forcibly aged. The samples are shaken for 24 hours to simulate the distribution channel and then stored dark at 40 0 C for 4 days. The tasting is fresh against forced. For sensory evaluation of the taste stability is according to the 5-point scheme of DLG tastes and in addition the aging state according to Eichhorn is evaluated with a 4-point scaling. As an alternative to accelerated aging, naturally stored beers (reserve samples) can and should be regularly tasted for aging.
Die Ergebnisse von DLG-Verkostung und Alterungsverkostung sind in er nachstehenden Tabelle dargestellt.The results of DLG tasting and aging tasting are shown in the table below.
Verkostung nach DLG:Tasting according to DLG:
Bewertung in Halbnotenschπtten von 1 bis 5 Bitte Aromaeindruck angeben 'Evaluation in half note grades from 1 to 5 Please specify flavor impression '
Alterungsverkostung:Aging Tasting notes:
1 = frisch Die Akzeptanz1 = fresh The acceptance
2 = leicht gealtert bezieht sich nur auf2 = slightly aged only refers to
3 = stark gealtert die Alterung des3 = strongly aged the aging of the
4 = extrem gealtert Bieres !4 = extremely aged beer!
Tabelle : Verkostung nach DLG und Alterungsverkostung nach Eichhorn Table: Tasting according to DLG and aging tasting according to Eichhorn
Tabelle 1 : AlterungsindikatorenTable 1: Aging indicators
OO OO
Tabelle 2: Höhere aliphatische Alkohole und leichtflüchtige EsterTable 2: Higher aliphatic alcohols and volatile esters
CD CD

Claims

Patentansprüche claims
1. Verfahren zur Verbesserung der wertbestimmenden Eigenschaften von biologischen fermentierten Lösungen, dadurch gekennzeichnet, dass man die bio- logisch fermentierte Lösung nach der Fermentation pro 100 Liter mit 1 bis 3000 g eines Polymerisates aus 50-99,5 Gew.% N-Vinylimidazol 0 bis 49,5 Gew.% eines anderen copolymerisierbaren Monomeren einpolymerisiert enthält und unter Ausschluß von Sauerstoff und von Polymerisationsinitiatoren sowie in Gegenwart von 0,5 bis 10 Gew. %, bezogen auf die Monomeren, eines Vernet- zers hergestellt wird, behandelt.1. A method for improving the value-determining properties of biological fermented solutions, characterized in that the biologically fermented solution after fermentation per 100 liters with 1 to 3000 g of a polymer of 50-99.5 wt.% N-Vinylimidazol 0 contains up to 49.5 wt.% of another copolymerizable monomer in copolymerized form and is prepared in the absence of oxygen and of polymerization initiators and in the presence of from 0.5 to 10% by weight, based on the monomers, of a crosslinking agent.
2. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass ein Polymerisat eingesetzt wird, das als Comonomer ausschließlich N-Vinylpryrrolidon oder N- Vinylcaprolactam oder eine Mischung von beiden einpolymerisiert enthält.2. The method according to claim 1, characterized in that a polymer is used which contains copolymerized as comonomer exclusively N-vinylpryrrolidone or N-vinylcaprolactam or a mixture of both.
3.Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass ein Polymerisat eingetzt wird, das als Vernetzter N, NT-Divinylehthlenharnstoff einpoly- merisat enthält.3.A method according to claim 1 or 2, characterized in that a polymer is used, which contains polymerized as crosslinked N, NT-divinylethurea urea.
4.Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass ein Polymerisat eingesetzt wird, das in Gegenwart eines Reduktionsmittels hergestellt wird.4.Verfahren according to any one of claims 1 to 3, characterized in that a polymer is used, which is prepared in the presence of a reducing agent.
δ.Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass ein Polymerisat eingesetzt wird, das in Gegenwart von Wasser bei 30 bis 1500C hergestellt worden ist.δ.A method according to any one of claims 1 to 4, characterized in that a polymer is used which has been prepared in the presence of water at 30 to 150 0 C.
Θ.Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass ein Polymerisat eingesetzt wird, das ohne Lösungsmittel bei 100 bis 2000C hergestellt worden ist.Θ.Process according to one of claims 1 to 5, characterized in that a polymer is used which has been prepared without solvent at 100 to 200 0 C.
7.Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass als biologisch fermentierte Lösung Bier oder bierähnliche Getränke behandelt werden.7.A method according to any one of claims 1 to 6, characterized in that be treated as a biologically fermented solution beer or beer-like drinks.
8. Verfahren nach einem der Ansprüche I bis 7, dadurch gekennzeichnet, dass die biologisch fermentierte Lösung ein Unfiltrat darstellt.8. The method according to any one of claims I to 7, characterized in that the biologically fermented solution is an unfiltrate.
Θ.Verfahren nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass das eingesetzte Polymer Bestandteil eines dynamischen oder statischen Filtrationsverfahrens ist. Θ.Process according to one of claims 1 to 8, characterized in that the polymer used is part of a dynamic or static filtration process.
10. Verfahren nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, dass das eingesetzte Polymer auch in den vorgeschalteten Produktionsprozessen Wasseraufbereitung, Maischen, Würzebehandlung, und Gärung zum Einsatz kommt .10. The method according to any one of claims 1 to 9, characterized in that the polymer used in the upstream production processes water treatment, mashing, wort treatment, and fermentation is used.
1 1. Verwendung eines Polymerisates aus 50-99,5 Gew.% N-Vinylimidazol 0 bis 49,5 Gew.% eines anderen copolymerisierbaren Monomeren einpolymeri- siert enthält und unter Ausschluß von Sauerstoff und von Polymerisationsinitiatoren sowie in Gegenwart von 0,5 bis 10 Gew. %, bezogen auf die Monomeren, eines Vernetzers hergestellt wird, zur Verbesserung der wertbestimmenden Eigenschaften von fermentierten Flüssigkeiten. 1 1. Use of a polymer of 50-99.5 wt.% N-Vinylimidazol 0 to 49.5 wt.% Of another copolymerizable monomer in copolymerized form and with the exclusion of oxygen and of polymerization initiators and in the presence of 0.5 to 10 wt.%, Based on the monomers, of a crosslinking agent is prepared, to improve the value-determining properties of fermented liquids.
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DE10253591A1 (en) * 2002-11-15 2004-05-27 Basf Ag Use of polymers of basic amino group-containing monomers, e.g. N-vinyl-imidazole, as additives for cosmetic, dermatological or pharmaceutical formulations, especially delayed-release salicylic acid preparations
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